CN113717487A

CN113717487A - Resin composition and product thereof

Info

Publication number: CN113717487A
Application number: CN202010646238.7A
Authority: CN
Inventors: 陈国盛; 徐景舷
Original assignee: Elite Material Co Ltd
Current assignee: Elite Material Co Ltd
Priority date: 2020-05-26
Filing date: 2020-07-07
Publication date: 2021-11-30
Also published as: TW202144485A; US20210371627A1; TWI739443B

Abstract

The invention discloses a resin composition, which comprises 100 parts by weight of polybutadiene and 10-40 parts by weight of maleimide resin, wherein: the polybutadiene has a 1, 2-vinyl content greater than or equal to 85%; the polybutadiene has a lithium ion content of less than or equal to 100 ppm; and the resin composition does not contain a polyphenylene ether resin. In addition, the invention also discloses a product prepared from the resin composition, which comprises a prepreg, a resin film, a laminated board or a printed circuit board.

Description

Resin composition and product thereof

Technical Field

The present invention relates to a resin composition, and more particularly, to a resin composition that can be used to prepare a prepreg, a resin film, a laminate or a printed circuit board.

Background

With the rapid development of the fifth generation mobile communication technology (5G), a resin material suitable for high-frequency and high-speed information transmission is also the main development direction of the substrate, so as to satisfy the requirement of maintaining an extremely low dielectric loss (dielectric loss measured at a frequency of 10GHz is less than or equal to 0.0025) under high temperature change and high humidity change, and at the same time, have a relative tracking index capable of passing high voltage test, and serve as an evaluation index of a high-specification laminated board.

Disclosure of Invention

In view of the problems encountered in the prior art, and in particular the inability of the prior art materials to meet one or more of the above-mentioned technical problems, it is a primary object of the present invention to provide a resin composition that overcomes at least one of the above-mentioned technical problems, and articles made using the resin composition.

In order to achieve the above object, the present invention discloses a resin composition comprising 100 parts by weight of polybutadiene and 10 to 40 parts by weight of maleimide resin, wherein: the polybutadiene has a 1, 2-vinyl content greater than or equal to 85%; the polybutadiene has a lithium ion content of less than or equal to 100 ppm; and the resin composition does not contain a polyphenylene ether resin.

For example, the polybutadiene is a polymer of butadiene, and is also an autopolymer of butadiene, and has a 1, 2-vinyl content of greater than or equal to 85%, such as a 1, 2-vinyl content of greater than or equal to 90%, such as a 1, 2-vinyl content of greater than or equal to 85% and less than or equal to 95%, such as a 1, 2-vinyl content of greater than or equal to 90% and less than or equal to 95%, and is not limited thereto. In addition, the lithium ion content of the polybutadiene is less than or equal to 100ppm, for example, the lithium ion content is between 1ppm and 100ppm, for example, between 10ppm and 100ppm, and not limited thereto.

For example, in one embodiment, the kind of the maleimide resin is not particularly limited and may include, but is not limited to, various maleimide resins known in the art, and specific examples include 4,4 ' -diphenylmethane bismaleimide, polyphenylmethane maleimide, bisphenol a diphenyl ether bismaleimide, 3 ' -dimethyl-5, 5 ' -diethyl-4, 4 ' -diphenylmethane bismaleimide, 3 ' -dimethyl-5, 5 ' -dipropyl-4, 4 ' -diphenylmethane bismaleimide, m-phenylene bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1, 6-bismaleimide- (2,2, 4-trimethyl) hexane, 2, 3-dimethylbenzylmaleimide, 2, 6-dimethylbenzylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide, a maleimide resin containing an aliphatic long chain structure, a prepolymer of a diallyl compound and a maleimide resin, a prepolymer of a diamine and a maleimide resin, a prepolymer of a polyfunctional amine and a maleimide resin, a prepolymer of an acidic phenol compound and a maleimide resin, or a combination thereof. Unless otherwise specified, the maleimide resin includes modifications of these components.

One of the main features of the resin composition is that it does not contain a polyphenylene ether resin. Herein, the polyphenylene ether resin means various polyphenylene ether resins commonly used for prepreg, resin film, laminate or printed circuit board fabrication, including but not limited to vinyl-containing polyphenylene ether resin, hydroxyl-containing polyphenylene ether resin …, and the like. Further, for example, in one embodiment, the resin composition is also free of one or all of a cyanate ester resin, an epoxy resin, and a phenol resin.

For example, in one embodiment, the foregoing resin composition further comprises an active ester, vinylbenzyl-dicyclopentadiene phenyl ether, bisvinylbenzyl ether, 1, 2-bis (vinylphenyl) ethane, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, 1,2, 4-trivinylcyclohexane, styrene maleic anhydride, an acrylate, a polyolefin, or a combination thereof. Unless otherwise specified, the above-mentioned components are to be interpreted as including modified forms of these components.

For example, in one embodiment, the foregoing resin composition further comprises a styrene-butadiene-divinylbenzene terpolymer, a hydrogenated styrene-butadiene-divinylbenzene terpolymer, a styrene-butadiene-maleic anhydride terpolymer, a hydrogenated styrene-butadiene-maleic anhydride terpolymer, a vinyl-polybutadiene-urethane oligomer, a styrene-butadiene copolymer, a hydrogenated styrene-butadiene copolymer, a styrene-isoprene copolymer, a hydrogenated styrene-isoprene copolymer, a maleic anhydride-butadiene copolymer, other polybutadienes, or combinations thereof.

For example, in one embodiment, the aforementioned resin composition further comprises a flame retardant, an inorganic filler, a hardening accelerator, a polymerization inhibitor, a solvent, a silane coupling agent, a surfactant, a coloring agent, a toughening agent, a core shell rubber, or a combination thereof.

Another main object of the present invention is to provide an article made of the aforementioned resin composition, which comprises a prepreg, a resin film, a laminate or a printed circuit board.

For example, in one embodiment, the article of manufacture described above has one, more, or all of the following characteristics:

a dielectric loss of 0.0025 or less as measured at a frequency of 10GHz with reference to the method described in JIS C2565;

water absorption of 0.1% or less as measured by IPC-TM-6502.6.2.1 a;

no tracking was produced as tested under voltage conditions of 600V with reference to the method described in ASTM D3638; and

the tack test can be passed on the prepreg.

Detailed Description

To enable those skilled in the art to understand the features and effects of the present invention, the general description and definitions of the terms and words used in the specification and claims are set forth below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.

The use of "a," "an," "the," or similar language herein to describe elements and features of the invention is made merely for convenience and to provide a general sense of the scope of the invention. Thus, the description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

In this context, "or a combination thereof" means "or any combination thereof", "any", or "any" means "any", or "any".

In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to refer to an open-ended franslational phrase (open-ended franslational phrase) that is intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Furthermore, in this document, the terms "comprising," "including," "having," "containing," and "containing" are to be construed as specifically disclosed and also cover both the closed connectors comprising "…," "consisting of," "the balance being," and the connectors comprising "consisting essentially of …," "consisting essentially of …," "consisting essentially of," "containing essentially of," "consisting essentially of …," "consisting essentially of," "containing essentially of," and the like.

All features or conditions, such as values, amounts and concentrations, defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual values (including integers and fractions) within the range, particularly integer values. For example, a description of a range of "1.0 to 8.0" or "between 1.0 and 8.0" should be considered to have been specifically disclosed for all subranges including 1.0 to 8.0, 1.0 to 7.0, 2.0 to 8.0, 2.0 to 6.0, 3.0 to 6.0, 4.0 to 8.0, 3.0 to 8.0, and the like, and should be considered to encompass the endpoints, particularly the subranges bounded by integer values, and to have been considered to have been specifically disclosed for individual values within the range, such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, and the like. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.

If an amount, concentration, or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, then it is understood that all ranges subsumed therein by any pair of the upper or preferred value of that range and the lower or preferred value of that range, regardless of whether ranges are separately disclosed. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

Numerical values herein are to be understood as having the precision of the numerical significance given the number of significant digits in question, provided that the resulting improved visual performance is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.

In this document, where Markush group (Markush group) or Option language is used to describe features or examples of the invention, those skilled in the art will recognize that subgroups of all members of the Markush group or Option list, or any individual member, may also be used to describe the invention. For example, if X is described as "selected from the group consisting of₁、X₂And X₃The group "also indicates that X has been fully described as X₁Is claimed with X₁And/or X₂And/or X₃Claim (5). Furthermore, to the extent that markush group or option language is used to describe features or examples of the invention, those skilled in the art will recognize that any combination of sub-groups of all members or individual members of the markush group or option list can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of₁、X₂And X₃Group consisting of "and Y is described as" selected from Y₁、Y₂And Y₃The group "formed indicates that X has been fully described as X ₁Or X₂Or X₃And Y is Y₁Or Y₂Or Y₃Claim (5).

Unless otherwise specified, in the present invention, the compound refers to a chemical substance formed by two or more elements connected by chemical bonds, including a small molecule compound and a high molecule compound, and is not limited thereto. The compounds herein are not limited to a single chemical species when read, but are to be construed as having the same composition or class of chemical species with the same properties.

Unless otherwise specified, in the present invention, a polymer refers to a product formed by polymerization of a monomer, and often includes an aggregate of a plurality of macromolecules, each macromolecule being formed by repeating connection of a plurality of simple structural units by covalent bonds, the monomer being a compound for synthesizing the polymer. The polymer may include, but is not limited to, a homopolymer (also referred to as an autopolymer), a copolymer, a prepolymer, and the like. By prepolymer is meant a polymer of lower molecular weight between the monomer and the final polymer. For example, in the present invention, the prepolymer of diallyl compound and maleimide resin refers to a product obtained by polymerizing diallyl compound and maleimide resin to a middle molecular weight state, wherein the molecular weight of the product is higher than that of diallyl compound and maleimide resin before reaction, but lower than that of the final product obtained after complete reaction, and the prepolymer contains reactive functional groups which can be further polymerized to obtain a higher molecular weight product which is completely crosslinked or hardened. The polymer of course includes oligomers, and is not limited thereto. The oligomer is also called oligomer, and is a polymer composed of 2-20 repeating units, usually 2-5 repeating units. For example, diene polymers, when read, include diene homopolymers, diene copolymers, diene prepolymers, and of course diene oligomers, and the like. Also, for example, in the present invention, the (meth) acrylate polymer includes a (meth) acrylate homopolymer, a (meth) acrylate copolymer, a (meth) acrylate prepolymer, and of course, includes a (meth) acrylate oligomer.

Unless otherwise specified, in the present invention, the term "resin" is a customary name for a synthetic polymer, and when read, may include a monomer, a polymer thereof, a combination of monomers, a combination of polymers thereof, or a combination of a monomer and a polymer thereof, and the like, and is not limited thereto. For example, "maleimide resin" in the present invention, when read, includes maleimide monomers, maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, and combinations of maleimide monomers and maleimide polymers.

For example, in the present invention, "vinyl-containing" when read includes vinyl, allyl, (meth) acrylate, or combinations thereof.

In the present invention, unless otherwise specified, the modified product (also referred to as "modified product") includes: a product obtained by modifying the reactive functional group of each resin, a product obtained by prepolymerization of each resin with other resins, a product obtained by crosslinking each resin with other resins, a product obtained by homopolymerization of each resin, a product obtained by copolymerization of each resin with other resins, and the like.

Unless otherwise specified, the unsaturated bond in the present invention refers to a reactive unsaturated bond, such as but not limited to an unsaturated double bond capable of undergoing a crosslinking reaction with other functional groups, such as but not limited to an unsaturated carbon-carbon double bond capable of undergoing a crosslinking reaction with other functional groups.

Unless otherwise specified, in the present invention, specific examples of acrylates and acrylonitriles are written in the form "(meth)" which, when read, is to be understood as including both methyl-containing and methyl-free cases, such as poly (meth) acrylates, which are to be read as including polyacrylates and polymethacrylates. Also for example, (meth) acrylonitrile is to be read as including acrylonitrile and methacrylonitrile.

Unless otherwise specified, the alkyl and alkenyl groups described herein are to be read as including the various isomers thereof. For example, propyl should be read to include n-propyl and isopropyl.

It should be understood that the features disclosed in the embodiments herein can be combined in any combination to form the technical solution of the present application, as long as the combination of the features is not contradictory.

Unless otherwise specified, parts by weight, as used herein, refers to parts by weight, which may be in any weight unit, such as, but not limited to, kilograms, grams, pounds, and the like. For example, 100 parts by weight of polybutadiene, which means that it may be 100 kg of polybutadiene or 100 lbs of polybutadiene.

The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary or the following detailed description or examples. The methods, reagents and conditions employed in the examples are, unless otherwise indicated, those conventional in the art.

Broadly, the present invention broadly discloses a resin composition comprising 100 parts by weight of polybutadiene and 10 to 40 parts by weight of a maleimide resin, wherein: the polybutadiene has a 1, 2-vinyl content greater than or equal to 85%; the polybutadiene has a lithium ion content of less than or equal to 100 ppm; and the resin composition does not contain a polyphenylene ether resin.

As known to those skilled in the art, polybutadiene is an autopolymer of butadiene. In the polymerization process, butadiene may be polymerized in the form of a monomer such as cis-1, 4-addition, trans-1, 4-addition or 1, 2-addition. The monomer units of the end product polybutadiene will therefore also contain cis-1, 4-addition units, trans-1, 4-addition units or 1, 2-addition units. As the first main component of the resin composition of the present invention, the polybutadiene described herein means one having a 1, 2-addition unit content of 85% or more of the total unit content, that is, the polybutadiene described herein has a 1, 2-vinyl content of 85% or more. In one embodiment, for example, the 1, 2-vinyl content of the foregoing polybutadiene is greater than or equal to 90%; in another embodiment, the 1, 2-vinyl content of the foregoing polybutadiene is greater than or equal to 85% and less than or equal to 95%; in still another embodiment, the polybutadiene has a 1, 2-vinyl content greater than or equal to 90% and less than or equal to 95%, and not limited thereto.

In addition, as known to those skilled in the art, generally, polybutadiene is produced by using a lithium-containing compound (e.g., n-butyllithium) as a polymerization initiator, and thus lithium ions remain in the polybutadiene product unless specifically purified. As the first main component of the resin composition of the present invention, the polybutadiene described in the present invention means one having a lithium ion content of 100ppm or less. In one embodiment, for example, the lithium ion content of the polybutadiene is between 1ppm and 100ppm, such as between 10ppm and 100ppm, and not limited thereto. In addition, if not specifically indicated, the content of lithium ions can be determined by any conventional metal ion measuring instrument, such as but not limited to a mass spectrometer.

One of the main features of the resin composition of the present invention is that it does not contain a polyphenylene ether resin. Herein, the polyphenylene ether resin means various polyphenylene ether resins commonly used for prepreg, resin film, laminate or printed circuit board fabrication, including but not limited to vinyl-containing polyphenylene ether resin, hydroxyl-containing polyphenylene ether resin …, and the like. Further, for example, in one embodiment, the resin composition is also free of one or all of a cyanate ester resin, an epoxy resin, and a phenol resin.

In certain embodiments, the resin composition of the present invention contains 10 to 40 parts by weight of the maleimide resin, such as, but not limited to, 10, 20 or 40 parts by weight of the maleimide resin, relative to 100 parts by weight of the polybutadiene.

As a second main component of the resin composition of the present invention, the maleimide resin of the present invention comprises a monomer, a polymer or a combination thereof having one or more maleimide functional groups in the molecule. The maleimide resin used in the present invention is not particularly limited, and may be any one or more maleimide resins suitable for prepreg (or prepreg), resin film, laminate or printed wiring board production, unless otherwise specified. In certain embodiments, maleimide resins comprising: 4,4 '-diphenylmethane bismaleimide (4, 4' -diphenylmethanebismaleimide), phenylmethane maleimide oligomer (or polyphenylmethane maleimide), bisphenol A diphenyl ether bismaleimide (bisphenone A diphenylether bismaleimide), 3 '-dimethyl-5, 5' -diethyl-4,4 '-diphenylmethane bismaleimide (3, 3' -dimethyl-5,5 '-dimethyl-4, 4' -diphenylmethanbismaleimide), or bis (3-ethyl-5-methyl-4-maleimidobenzene) methane (bis- (3-ethyl-5-methyl-4-maleimidophenyl)), 3 '-dimethyl-5, 5' -dipropyl-4,4 '-diphenylmethane bismaleimide (3, 3' -dimethyl-5,5 '-Dipropylene-4, 4' -diphenylmethylene-bis-maleimide), m-phenylenebismaleimide (m-phenylenebismaleimide), 4-methyl-1, 3-phenylenebismaleimide (4-methyl-1, 3-phenylenebismaleimide), 1,6-bismaleimide- (2,2,4-trimethyl) hexane (1,6-bismaleimide- (2,2, 4-trimethyi) hexane), 2, 3-dimethylbenzylmaleimide (N-2, 3-xylmaleimide), 2, 6-dimethylbenzylmaleimide (N-2, 6-xylmaleimide), N-phenylmaleimide (N-phenylvinylbenzylmaleimide), vinylbenzylmaleimide (benzylmaleimide, VBM), maleimide resins containing aliphatic long chain structures, prepolymers of diallyl compounds and maleimide resins, prepolymers of diamines and maleimide resins, prepolymers of polyfunctional amines and maleimide resins, prepolymers of acidic phenol compounds and maleimide resins, or combinations thereof. Unless otherwise specified, the maleimide resin includes modifications of these components.

For example, the maleimide resin may be a maleimide resin produced by Daiwakasei Industry under the trade name BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000H, BMI-4000, BMI-5000, BMI-5100, BMI-TMH, BMI-7000, and BMI-7000H, or a maleimide resin produced by K.I chemical company under the trade name BMI-70, BMI-80, and the like.

For example, the maleimide resin containing an aliphatic long chain structure may be a maleimide resin produced by designer molecular companies under the trade names BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000.

In one embodiment, for example, the resin composition of the present invention may also optionally further comprise an active ester, vinylbenzyl-dicyclopentadiene phenyl ether, bisvinylbenzyl ether, 1, 2-bis (vinylphenyl) ethane, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, 1,2, 4-trivinylcyclohexane, styrene maleic anhydride, an acrylate, a polyolefin, or a combination thereof. Unless otherwise specified, the above-mentioned components are to be interpreted as including modified forms of these components. Unless otherwise specified, the content of any of the above-mentioned components may be 1 to 100 parts by weight, for example, 1 to 50 parts by weight, relative to 100 parts by weight of the aforementioned polybutadiene, and the proportional relationship therebetween may be adjusted as necessary.

In one embodiment, for example, the reactive esters suitable for use in the present invention can be various types of reactive polyester resins known in the art, including but not limited to various commercially available reactive polyester resin products. Such as but not limited to, the reactive polyester resins sold by Dainippon ink chemistry under the trade names HPC-8000, HPC-8150.

In one embodiment, for example, examples of vinylbenzyl-dicyclopentadiene phenyl ethers suitable for use in the present invention are not particularly limited, such as but not limited to the structures shown below:

wherein R is₆Each independently represents hydrogen, a straight chain alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms; n is an integer of 1 to 10; preferably, R₆Is hydrogen or methyl, and n is an integer of 1 to 3.

The bisvinylbenzyl ether, 1, 2-bis (vinylphenyl) ethane, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, 1,2, 4-trivinylcyclohexane and styrene suitable for use in the present invention are not particularly limited and may include various commercially available products.

In one embodiment, for example, the ratio of styrene (S) to Maleic Anhydride (MA) suitable for use in the present invention may be 1:1, 2:1, 3:1, 4:1, 6:1, 8:1 or 12:1, such as styrene maleic anhydride resins sold by Cray Valley under the trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60 and EF-80, or styrene maleic anhydride copolymers sold by Polyscope under the trade names C400, C500, C700 and C900, without limitation.

In one embodiment, for example, the acrylate suitable for use in the present invention is not particularly limited, and acrylate compounds having two or more unsaturated bonds in the molecular structure are suitable, and various monofunctional acrylates that are commercially available may also be included.

In one embodiment, for example, the polyolefins suitable for use in the present invention are not particularly limited, and can be any one or more commercially available products, self-made products, or combinations thereof, such as, but not limited to, styrene-butadiene-divinylbenzene terpolymers, hydrogenated styrene-butadiene-divinylbenzene terpolymers, styrene-butadiene-maleic anhydride terpolymers, hydrogenated styrene-butadiene-maleic anhydride terpolymers, vinyl-polybutadiene-urea ester oligomers, styrene-butadiene copolymers, hydrogenated styrene-butadiene copolymers, styrene-isoprene copolymers, hydrogenated styrene-isoprene copolymers, maleic anhydride-butadiene copolymers, other polybutadienes (other types of polybutadienes other than the aforementioned polybutadienes), or combinations thereof. For example, in one embodiment, the amount of any of the above polyolefins may be 10 to 20 parts by weight relative to 100 parts by weight of the polybutadiene.

Furthermore, the resin composition of the present invention may further optionally include a flame retardant, an inorganic filler, a hardening accelerator, a polymerization inhibitor, a solvent, a silane coupling agent, a surfactant, a coloring agent, a toughening agent, a core shell rubber, or a combination thereof, in addition to the aforementioned components.

In one embodiment, for example, the flame retardant suitable for use in the present invention may be any one or more flame retardants suitable for use in prepreg, resin film, laminate or printed circuit board fabrication, such as but not limited to, phosphorus-containing flame retardants, preferably including: ammonium polyphosphate (ammonium polyphosphate), hydroquinone-bis- (diphenylphosphate) (hydroquinone bis- (diphenylphosphate)), tris (2-carboxyethyl) phosphine (tri (2-carboxyxyethyl) phosphine, TCEP), tris (chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), resorcinol bis- (dimethylphenyl phosphate) (resorcinol bis (dihydroxyphenyl phosphate), RDXP (commercially available products such as PX-200, PX-201, PX-202), phosphazene compounds (phosphazene, commercially available products such as SPB-100, SPH-100, SPV-100, melamine polyphosphate (melamine polyphosphate), 9-10-dihydrophenanthrene phosphate (9, 10-dihydrophenanthrene phosphate), 10-dihydro-9-oxa-10-phenylphenanthrene-10-oxide, DOPO) and its derivatives (e.g., bis DOPO compounds) or resins, diphenylphosphine oxide (DPPO) and its derivatives (e.g., bis DPPO compounds) or resins, melamine cyanurate (melamine cyanurate), tris-hydroxy isocyanurate (tris-hydroxy isocyanurate), aluminum phosphinate (e.g., OP-930, OP-935, etc.), or combinations thereof.

For example, the flame retardant may be DPPO compound (e.g., double DPPO compound), DOPO compound (e.g., double DOPO compound), DOPO resin (e.g., DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), DOPO-bonded epoxy resin, etc., wherein the DOPO-PN is DOPO phenol novolac resin, the DOPO-BPN may be DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac), etc., bisphenol-phenol novolac resin.

The amount of the flame retardant is not particularly limited, if not specifically indicated, and may be 1 to 100 parts by weight, for example, 1 to 50 parts by weight, and for example, 30 to 50 parts by weight, relative to 100 parts by weight of the polybutadiene of the present invention.

The inorganic filler suitable for the present invention may be any one or more inorganic fillers suitable for prepreg, resin film, laminate or printed circuit board fabrication, and specific examples include, but are not limited to: silica (molten, non-molten, porous or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, silicon nitride or calcined kaolin. In addition, the inorganic filler may be in the form of spheres, fibers, plates, granules, flakes, or whiskers, and may optionally be pretreated with a silane coupling agent.

The amount of the above-mentioned inorganic filler is not particularly limited, if not specifically indicated, with respect to 100 parts by weight of the polybutadiene of the present invention, and may be 10 parts by weight to 400 parts by weight, for example, 50, 100, 150, 200, 250, 300 or 350 parts by weight.

Hardening accelerators suitable for use in the present invention may include Lewis bases or Lewis acids and like catalysts. Among them, the lewis base may include imidazole (imidazole), boron trifluoride amine complex, ethyltriphenylphosphonium chloride (ethylimphenylphosphonium chloride), 2-methylimidazole (2-methylimidazole, 2MI), 2-phenylimidazole (2-phenyl-1H-imidazolidone, 2PZ), 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole, 2E4MI), Triphenylphosphine (TPP), and 4-dimethylaminopyridine (4-dimethylaminopyridine, DMAP), or a combination thereof. The lewis acid may include metal salt compounds such as manganese, iron, cobalt, nickel, copper, zinc, etc., metal catalysts such as zinc octoate, cobalt octoate, etc. The hardening accelerator also includes hardening initiators, such as peroxides that can generate free radicals, including but not limited to: dibenzoyl peroxide (BPO), dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne (25B), di-t-butyl peroxide, di (t-butylperoxyisopropyl) benzene, di (t-butylperoxy) phthalate, di (t-butylperoxy) isophthalate, t-butyl peroxybenzoate, 2-bis (t-butylperoxy) butane, 2-bis (t-butylperoxy) octane, 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane, lauroyl peroxide, t-hexyl peroxypivalate, dibutylperoxyisopropylbenzene, and bis (4-t-butylcyclohexyl) peroxydicarbonate, or a combination thereof.

If not specifically indicated, the amount of the hardening accelerator used in the present invention may be adjusted as needed, for example, but not limited to, the amount of the hardening accelerator may be 0.01 to 20 parts by weight, preferably 5 to 20 parts by weight, relative to 100 parts by weight of the polybutadiene of the present invention.

The polymerization inhibitor of the present invention has an effect of inhibiting polymerization, and specific examples thereof are not particularly limited and may include various molecular type polymerization inhibitors, stable free radical type polymerization inhibitors or combinations thereof known in the art. For example, molecular type polymerization inhibitors suitable for use in the present invention include, but are not limited to, phenolic compounds, quinone compounds, arylamine compounds, aromatic nitro compounds, sulfur-containing compounds, variable valence metal chlorides, or combinations thereof. More specifically, molecular type polymerization inhibitors suitable for use in the present invention include, but are not limited to, phenol, hydroquinone, 4-t-butylcatechol, benzoquinone, chloranil, 1, 4-naphthoquinone, trimethylquinone, aniline, nitro groupBenzene and Na₂S、FeCl₃、CuCl₂Or a combination thereof. For example, stable free radical type polymerization inhibitors suitable for use in the present invention include, but are not limited to, 1-diphenyl-2-trinitrophenylhydrazine (DPPH), triphenylmethyl, or combinations thereof.

The amount of the polymerization inhibitor used in the present invention may be adjusted as necessary, if not specifically indicated, and for example, but not limited thereto, the amount of the polymerization inhibitor may be 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of the polybutadiene of the present invention.

The main functions of the solvent added in the invention are to dissolve each component in the resin composition, change the solid content of the resin composition and adjust the viscosity of the resin composition. For example, the solvent may include, but is not limited to, methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, or a mixture thereof.

Silane coupling agents suitable for use in the present invention may include silane compounds (silanes, such as, but not limited to, siloxane compounds (siloxane)), which may be further classified according to the type of functional group into amino silane compounds (amino silanes), epoxy silane compounds (epoxy silanes), vinyl silane compounds, ester silane compounds, hydroxy silane compounds, isocyanatosilane compounds, methacryloxy silane compounds, and acryloxy silane compounds.

The main effect of the surfactant added in the present invention is to uniformly disperse the inorganic filler in the resin composition.

Colorants suitable for use in the present invention may include, but are not limited to, dyes (dye) or pigments (pigment).

The main effect of the added toughening agent is to improve the toughness of the resin composition. The toughening agent may include, but is not limited to, rubbers such as carboxyl-terminated butadiene nitrile rubber (CTBN).

The resin composition of the embodiments of the present invention can be made into various articles by various processing methods, including but not limited to a prepreg, a resin film, a laminate or a printed circuit board.

For example, the resin composition of the present invention can be prepared into a prepreg.

In one embodiment, the prepreg according to the present invention includes a reinforcing material and a laminate disposed on the reinforcing material, wherein the laminate is formed by heating the resin composition to a semi-cured state (B-stage) at a high temperature. The baking temperature for producing the prepreg is, for example, 140 ℃ to 170 ℃. The reinforcing material may be any one of a fiber material, a woven fabric, and a non-woven fabric, and the woven fabric preferably includes a glass fiber cloth. The type of the glass fiber cloth is not particularly limited, and may be commercially available glass fiber cloth that can be used for various printed circuit boards, such as E-type glass fiber cloth, D-type glass fiber cloth, S-type glass fiber cloth, T-type glass fiber cloth, L-type glass fiber cloth, or Q-type glass fiber cloth, wherein the type of the fiber includes yarn, roving, and the like, and the form may include open fiber or non-open fiber. The non-woven fabric preferably includes a liquid crystal resin non-woven fabric such as a polyester non-woven fabric, a polyurethane non-woven fabric, and the like, but is not limited thereto. The fabric may also include a liquid crystal resin fabric, such as a polyester fabric or a polyurethane fabric, and is not limited thereto. The reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material may also optionally be pretreated with a silane coupling agent. The insulating layer is formed after the prepreg is subsequently heated and cured (C-stage).

In one embodiment, the resin compositions are uniformly mixed to form a varnish (also called a varnish), the varnish is placed in an impregnation tank, the glass fiber cloth is immersed in the impregnation tank, the resin compositions are attached to the glass fiber cloth, and the mixture is heated and baked at a proper temperature to be in a semi-cured state, so that a prepreg can be obtained.

For example, the resin composition of the present invention can also be made into a resin film, and the resin film is formed by baking and heating the resin composition to a semi-cured state. For example, the resin composition may be selectively coated on a liquid crystal resin film, a polyethylene terephthalate film (PET film), or a polyimide film (polyimide film), and then heated and baked at a suitable heating temperature to a semi-cured state to form the resin film. For example, the resin composition according to each embodiment of the present invention may be coated on a copper foil to uniformly adhere the resin composition, and then baked at an appropriate temperature to a semi-cured state to obtain a resin film.

For example, the resin composition of the present invention can be made into various laminates, which comprise at least two metal foils and at least one insulating layer disposed between the two metal foils, and the insulating layer can be formed by curing the resin composition at high temperature and high pressure (C-stage), wherein the curing temperature is, for example, between 190 ℃ and 240 ℃, preferably between 190 ℃ and 230 ℃, the curing time is 60 to 180 minutes, preferably 60 to 150 minutes, and the curing pressure is 400 to 800psi, preferably 600 to 700 psi. The insulating layer may be obtained by curing the prepreg or the resin film. The metal foil may be made of copper, aluminum, nickel, platinum, silver, gold, or an alloy thereof, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate.

In one embodiment, the laminate may be further processed into a printed circuit board.

For example, one way of manufacturing the printed circuit board of the present invention may be to use a double-sided copper clad laminate (e.g., product EM-891, available from taiwan optoelectronics materials) having a copper foil of 1 ounce hvlp (super low profile) with a thickness of 28 mils (mil) and to form electrical continuity between the upper and lower copper foils by drilling and electroplating. And etching the upper layer copper foil and the bottom layer copper foil to form an inner layer circuit. And then performing brown coarsening treatment on the inner layer circuit, so that a concave-convex structure is formed on the surface to increase the roughness. Then, the copper foil, the prepreg, the inner layer circuit board, the prepreg and the copper foil are sequentially stacked, and then heated for 60 to 180 minutes at a temperature of 190 to 240 ℃ by using a vacuum laminating device to cure the insulating layer material of the prepreg. Then, various circuit board processes known in the art, such as blackening, drilling, copper plating, etc., are performed on the copper foil on the outermost surface to obtain a printed circuit board.

In one embodiment, the resin composition provided by the invention can improve at least one of the characteristics of dielectric loss, water absorption, tracking, prepreg stickiness and the like of an article.

For example, articles made from the resin compositions provided herein may satisfy one, more, or all of the following characteristics:

water absorption of 0.1% or less as measured by IPC-TM-6502.6.2.1 a;

the tack test can be passed on the prepreg.

The resin compositions of the examples of the present invention and the comparative examples of the present invention were prepared from the following raw materials in the amounts shown in tables 1 to 4, respectively, and further prepared into various test samples.

The chemical raw materials and the code numbers used in the examples of the invention and the comparative examples are as follows:

a-1: polybutadiene having a 1, 2-vinyl content of 85% or more and a lithium ion content of 100ppm or less, with the trade name B-1000, available from Nippon soda.

A-2: polybutadiene having a 1, 2-vinyl content of greater than or equal to 90% and a lithium ion content of less than or equal to 100ppm, available under the trade name B-3000 from Nippon Cao.

A-3: polybutadiene having a 1, 2-vinyl content greater than or equal to 90% and a lithium ion content greater than 300ppm, available from Cray Valley under the trade designation Ricon 154.

A-4: polybutadiene having a1, 2-vinyl content equal to 70%, available under the trade name Ricon 150 from Cray Valley.

A-5: polybutadiene with a1, 2-vinyl content equal to 28%, available under the trade name Ricon 131 from Cray Valley.

B-1: 3,3 ' -dimethyl-5, 5 ' -diethyl-4, 4 ' -diphenylmethane bismaleimide, trade name BMI-5100, available from Daohuazai.

B-2: bisphenol A diphenyl ether bismaleimide, trade name BMI-4000, was purchased from Dazai.

B-3: polyphenylmethaneimide, trade name BMI-2300, is available from Dazhou chemical industries.

B-4: a maleimide resin containing an aliphatic long chain structure, having the trade name BMI-3000, was purchased from designer molecular Co.

H-1: the vinylbenzylpolyphenylene ether resin, having the trade name OPE-2st 2200, was purchased from Mitsubishi gas chemistry.

H-2: methacrylate polyphenylene ether resin, trade name SA9000, available from Sabic.

H-3: hydroxy polyphenylene ether resin, trade name SA120, available from Sabic.

A-6: styrene-butadiene copolymer, with a1, 2-vinyl content equal to 70%, with the trade name Ricon 100, available from Cray Valley.

A-7: styrene-butadiene copolymer, with a1, 2-vinyl content equal to 30%, with the trade name Ricon 184, available from Cray Valley.

A-8: styrene-butadiene-divinylbenzene terpolymer, available under the trade name Ricon 257 from Cray Valley.

A-9: styrene-butadiene copolymer, tradename D-1118, is available from Kraton.

A-10: hydrogenated styrene-butadiene copolymer, tradename H1052, available from Asahi KASEI.

C-1: spherical silica, sold under the trade name SC2500-SXJ, is available from Admatechs corporation.

D-1: a hardening accelerator, dicumyl peroxide, commercially available.

E-1: polymerization inhibitor, 4, 4' -butylidenebis (6-tert-butyl-3-methylphenol), commercially available.

F-1: flame retardant, tradename 8010, available from yabao corporation.

F-2: flame retardant, product name BT-93, available from Yabao corporation.

G-1: the solvent, the mixed solvent of toluene and butanone, the weight ratio of toluene and butanone is 50:50, and the solvent is prepared by self. In the table, "proper amount" represents the amount of solvent added in an amount sufficient to dissolve all of the maleimide resin, the curing accelerator and the polymerization inhibitor.

The compositions (units are parts by weight) and the characteristics of the resin compositions of the examples and comparative examples are shown in the following table:

TABLE 1 composition (unit: parts by weight) and characteristic test of resin compositions of examples

TABLE 2 composition (unit: parts by weight) and characteristic test of resin compositions of comparative examples

TABLE 3 composition (unit: parts by weight) and characteristic test of resin compositions of comparative examples

TABLE 4 composition (unit: parts by weight) and characteristic test of resin compositions of comparative examples

The aforementioned characteristics were obtained by preparing a specimen (sample) in the following manner and analyzing the characteristics according to specific conditions.

1. Prepreg preparation: the resin compositions of the examples (table 1) and the comparative examples (tables 2 to 4) were selected, respectively, and the respective resin compositions were uniformly mixed to form a varnish (also called as a liquid cement (varnish)), the varnish was placed in an immersion tank, and a glass fiber cloth (for example, 1080-sized L-glass fiber cloth (available from Asahi corporation) was immersed in the immersion tank to attach the resin compositions to the glass fiber cloth, and the resin compositions were heated at 140 to 160 ℃ to be in a semi-cured state (B-Stage), thereby obtaining a prepreg having a resin content of about 70%.

2. Copper-free substrates (2-ply, two prepregs laminated): two pieces of ultra low surface roughness (HVLP) copper foil with a thickness of 18 μm and two pieces of 1080L-glass fiber cloth were prepared to impregnate prepregs obtained from each sample to be tested (each set of examples or comparative examples), the copper foil, the two pieces of prepregs, and the copper foil were stacked in this order, and the substrates were pressed and cured for 1 hour under vacuum conditions at a pressure of 600psi and a temperature of 230 ℃ to form copper foil-containing substrates (2-ply, two prepregs were pressed). And then, etching the copper foil substrate to remove the copper foils on the two sides to obtain a copper-free substrate (2-ply), wherein the copper-free substrate is formed by laminating two prepregs, and the resin content of the copper-free substrate (2-ply) is about 70%.

3. Copper-free substrates (8-ply, pressed from eight prepregs): two pieces of 18 μm thick ultra low surface roughness (HVLP) copper foil and eight pieces of 1080L-glass fiber cloth were prepared to impregnate the prepregs obtained from each sample to be tested (each set of examples or comparative examples), the copper foil, the eight prepregs and the copper foil were stacked in this order, and the substrates were pressed and cured under vacuum conditions at 600psi and 230 ℃ for 1 hour to form copper foil-containing substrates (8-ply, eight prepregs). Then, the copper foil substrate was etched to remove the copper foils on both sides, to obtain a copper-free substrate (8-ply) having a resin content of about 70%.

4. A copper-free substrate (formed by laminating eighteen prepregs, 18-ply): two pieces of 18 μm thick ultra low surface roughness (HVLP) copper foil and eighteen pieces of 1080L-glass fiber cloth were prepared to impregnate each prepreg prepared by the sample to be tested (each set of examples or comparative examples), the copper foil, the eighteen prepreg and the copper foil were stacked in this order, and the substrates were pressed and cured under vacuum conditions at 600psi and 230 ℃ for 1 hour to form copper foil-containing substrates (18-ply, eighteen prepregs). Then, the copper foil substrate was etched to remove the copper foils on both sides, to obtain a copper-free substrate (18-ply) having a resin content of about 70%.

For the sample to be tested, the test methods and the analysis items of the characteristics are as follows:

dielectric loss (Df)

In the measurement of dielectric loss, the above copper-free substrate (2-ply) was selected as a sample to be measured, and each sample to be measured was measured at a frequency of 10GHz using a microwave dielectric analyzer (available from AET, Japan) by the method described in JIS C2565 Measuring methods for transfer ceramics for microwave device. Lower dielectric loss represents better dielectric properties of the sample to be tested. Under the condition that the Df value is less than 0.0030 and the measuring frequency is 10GHz, the difference of the Df values is less than 0.0002 represents that the dielectric loss of the substrates has no significant difference, and the difference of the Df values is greater than or equal to 0.0002 represents that the dielectric loss of different substrates has significant difference. The Df value is unitless. For example, the dielectric loss of an article made from the resin composition disclosed herein is less than or equal to 0.0020, such as between 0.0015 and 0.0020, as measured by the method described in JIS C2565.

Water absorption rate

In the water absorption test, referring to the method described in IPC-TM-6502.6.2.1 a, a copper-free substrate (formed by pressing eight prepregs) with a length of 2 inches and a width of 2 inches is selected as a sample to be tested, each sample to be tested is put into an oven with a temperature of 105 ± 10 ℃ to be baked for 1 hour and then taken out, the sample is cooled at room temperature (about 25 ℃) for 10 minutes and then weighed to obtain W1, then the weighed copper-free substrate is put into pure water at room temperature to be soaked for 24 hours and then taken out, residual water on the surface of the substrate is wiped, the weighed weight after wiping is W2 after water absorption, and the formula is as follows: the water absorption W (%) ((W2-W1)/W1) × 100% was calculated. The water absorption is expressed in%.

For example, articles made from the resin compositions disclosed herein have a water absorption of less than or equal to 0.1%, such as between 0.10% and 0.05%, as measured by the method described with reference to IPC-TM-6502.6.2.1 a.

Relative tracking index (CTI)

The copper-free substrate (formed by pressing eighteen prepregs) is selected as a sample to be measured (the size is 100mm in length, 100mm in width and 3mm in height), and each sample to be measured is measured by referring to the method described in ASTM D3638. After applying a voltage of 100V to the sample on the test apparatus, 1 drop of 0.1 wt% ammonium chloride aqueous solution was added dropwise every 30 seconds, and the number of drops added until tracking occurred was measured by continuous titration. If no leakage tracking is generated after more than 50 drops, the voltage is adjusted to 50V to 150V, the voltage value which can be borne by the sample is tested, and the voltage is adjusted to 50V for each time, and the voltage testing range is from 100V to 600V. The relative tracking index is expressed in volts (abbreviated as V). A voltage difference greater than or equal to 5V is a significant difference. If the test is at 600V and more than 50 drops still do not produce tracking, it is indicated as "pass". If the voltage value fails below 600V (leakage tracking occurs) or fails at 600V, it is labeled "fail".

Tackiness (degree of resin peeling off from prepreg surface)

Cutting the prepregs into 10 sheets with the size of 21cm multiplied by 30cm, stacking the sheets in order, putting the sheets into an aluminum foil packaging bag for vacuum packaging, then putting the aluminum foil packaging bag into a thermostat with the temperature of 30 ℃ for 72 hours, then taking out the 10 sheets of prepregs, and carrying out single prepreg peeling. The specific implementation mode is as follows: the 10 prepregs are integrally erected at the same time, a weight of 10 g is clamped at any corner above the outermost one prepreg, and the outermost one prepreg is peeled from the other 9 prepregs under the action of gravity. The peel time was recorded from the start of clamping and releasing the weight to the end of complete peeling of the outermost prepreg (visual inspection by personnel). The 5 sets of data were averaged and a pass was recorded if the 5 sets of data averaged less than or equal to 10 seconds. Otherwise, if the average of 5 sets of data is greater than or equal to 10 seconds, the record is failure.

From the above test results, the following phenomenon can be observed.

Examples E1 to E7, in which 100 parts by weight of polybutadiene (1, 2-vinyl content: 85% or more and lithium ion content: 100ppm or less) according to the present invention and 10 parts by weight to 40 parts by weight of maleimide resin were used together in the resin composition, passed both the relative tracking index test and the prepreg tackiness test.

Comparative examples C1 and C2 in which the amount of the maleimide resin added falls outside the range of 10 to 40 parts by weight, and comparative examples C3 and C4 in which no maleimide resin is added, failed both the relative tracking index test and the prepreg tack test, and comparative example C2 also had a problem of excessively high water absorption, compared to examples E1 to E7.

Comparative examples C5 and C6 in which 20 parts by weight of a polyphenylene ether resin was added without adding a maleimide resin and comparative examples C7 to C9 in which 20 parts by weight of a maleimide resin and 20 parts by weight of a polyphenylene ether resin were added simultaneously failed to pass both the relative tracking index test and the prepreg tack test, compared with examples E1 to E7.

Comparative examples C10 to C11 using the same 100 parts by weight of polybutadiene having a 1, 2-vinyl content of less than 85% and comparative example C12 using the same 100 parts by weight of polybutadiene having a 1, 2-vinyl content of 85% or more and a lithium ion content of more than 300ppm as compared with examples E1 to E7 failed both the relative tracking index test and the prepreg tack test.

In comparison with examples E1 to E7, comparative examples C13 to C15, which used the same amount of other polyolefins (e.g., styrene-butadiene copolymer or hydrogenated styrene-butadiene copolymer) of 100 parts by weight, failed to pass both the relative tracking index test and the prepreg tack test, and comparative example C14 also had the problem of too high water absorption.

In comparison with examples E1 to E7, comparative example C16, which is likewise 100 parts by weight of polybutadiene having a 1, 2-vinyl content of less than 85% and contains other polyolefins but no maleimide resin, failed to pass both the relative tracking index test and the prepreg tack test.

Comparative example C17, which contained 20 parts by weight of maleimide resin, 40 parts by weight of other polyolefin and 100 parts by weight of polyphenylene ether resin, failed to pass both the relative tracking index test and the prepreg tack test, compared to examples E1 to E7.

Furthermore, as compared with examples E1 to E7, it was found from comparative examples C18 and C19 that even if the resin composition contains the polybutadiene (1, 2-vinyl content 85% or more and lithium ion content 100ppm or less) of the present invention and the maleimide resin and does not contain the polyphenylene ether resin, if the range or ratio of the amount of the polybutadiene to the amount of the maleimide resin in the resin composition does not meet the specific requirements, the relative tracking index test and the prepreg tackiness test cannot be simultaneously passed.

In general, the resin composition of the present invention can pass the relative tracking index test and the prepreg tack test at the same time. In addition, the resin composition of the present invention may satisfy one, more or all of the following characteristics: a dielectric loss of 0.0025 or less as measured at a frequency of 10GHz with reference to the method described in JIS C2565; water absorption of 0.1% or less as measured by IPC-TM-6502.6.2.1 a; no tracking was produced as tested under voltage conditions of 600V with reference to the method described in ASTM D3638; and may pass the prepreg tack test.

The above embodiments are merely exemplary in nature and are not intended to limit the claimed embodiments or the application or uses of such embodiments. In this document, the term "exemplary" represents "as an example, instance, or illustration. Any exemplary embodiment herein is not necessarily to be construed as preferred or advantageous over other embodiments.

Further, while at least one exemplary embodiment or comparative example has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations are possible. It should also be appreciated that the embodiments described herein are not intended to limit the scope, applicability, or configuration of the claimed subject matter in any way. Rather, the foregoing implementations will provide those skilled in the art with a convenient road map for implementing the described embodiment or embodiments. Also, various changes may be made in the function and arrangement of elements without departing from the scope defined in the claims, which includes known equivalents and all foreseeable equivalents at the time of filing this patent application.

Claims

1. A resin composition comprising 100 parts by weight of polybutadiene and 10 to 40 parts by weight of a maleimide resin, characterized in that:

The polybutadiene has a 1, 2-vinyl content greater than or equal to 85%;

the polybutadiene has a lithium ion content of less than or equal to 100 ppm; and

the resin composition does not contain a polyphenylene ether resin.

2. The resin composition of claim 1, wherein the maleimide resin comprises 4,4 ' -diphenylmethane bismaleimide, polyphenylmethane maleimide, bisphenol A diphenylether bismaleimide, 3 ' -dimethyl-5, 5 ' -diethyl-4, 4 ' -diphenylmethane bismaleimide, 3 ' -dimethyl-5, 5 ' -dipropyl-4, 4 ' -diphenylmethane bismaleimide, m-phenylene bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1, 6-bismaleimide- (2,2, 4-trimethyl) hexane, 2, 3-dimethylbenzene maleimide, 2, 6-dimethylbenzene maleimide, or mixtures thereof, N-phenylmaleimide, vinylbenzylmaleimide, a maleimide resin containing aliphatic long chain structures, a prepolymer of a diallyl compound and a maleimide resin, a prepolymer of a diamine and a maleimide resin, a prepolymer of a polyfunctional amine and a maleimide resin, a prepolymer of an acidic phenol compound and a maleimide resin, or a combination thereof.

3. The resin composition of claim 1, further comprising an active ester, vinylbenzyl-dicyclopentadiene phenyl ether, bisvinylbenzyl ether, 1, 2-bis (vinylphenyl) ethane, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, 1,2, 4-trivinylcyclohexane, styrene maleic anhydride, an acrylate, a polyolefin, or combinations thereof.

4. The resin composition of claim 3, wherein the polyolefin comprises a styrene-butadiene-divinylbenzene terpolymer, a hydrogenated styrene-butadiene-divinylbenzene terpolymer, a styrene-butadiene-maleic anhydride terpolymer, a hydrogenated styrene-butadiene-maleic anhydride terpolymer, a vinyl-polybutadiene-urea ester oligomer, a styrene-butadiene copolymer, a hydrogenated styrene-butadiene copolymer, a styrene-isoprene copolymer, a hydrogenated styrene-isoprene copolymer, a maleic anhydride-butadiene copolymer, other polybutadienes, or combinations thereof.

5. The resin composition of claim 1, further comprising a flame retardant, an inorganic filler, a hardening accelerator, a polymerization inhibitor, a solvent, a silane coupling agent, a surfactant, a colorant, a toughening agent, a core shell rubber, or a combination thereof.

6. An article made from the resin composition of claim 1, characterized by comprising a prepreg, a resin film, a laminate or a printed circuit board.

7. The article of claim 6, wherein no tracking occurs when tested at a voltage of 600V according to ASTM D3638.

8. The article of claim 6, wherein the article passes the prepreg tack test.